CN102560601A - Preparation method for microarc oxidation/hydrothermal treatment composite film on surface of magnesium alloy - Google Patents
Preparation method for microarc oxidation/hydrothermal treatment composite film on surface of magnesium alloyDownload PDFInfo
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Abstract
Translated fromChinese
Description
Technical field
The present invention relates to the preparation method of a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film.
Background technology
Multiple metal-based biomaterial since 20th century (like stainless steel, vitallium, titanium alloy and nickel-titanium shape memory material etc.) is by successfully exploitation; And wherein some biological hard tissue embedded material has been actually used in clinical; Wearing and tearing and the corrosion of these materials in tissue; Possibly produce harmful abrasive dust and metallic cation, even make component failure.Relative polymkeric substance or stupalith, magnesium alloy materials has many outstanding features.1. safe: magnesium is the major element that is only second to calcium, sodium and potassium in the human body, and everyone the daily requirement amount of being grown up surpasses 350mg[, and excessive magnesium can excrete through urine, so magnesium can not produce detrimentally affect to human body when degrading with given pace.2. have biological characteristics: magnesium is a kind of important element that can activate plurality of enzymes, is again energy transhipment, the key element storing and utilize, for the growth of regulating cell with keep membrane structure and play an important role.3. have degradability: magnesium can be degraded by human body fully.4. mechanical compatibility is good: the density of magnesiumalloy is suitable with people's bone density, and has higher specific tenacity and specific rigidity; Can be through regulating the Young's modulus that technology obtains and people's bone photo is worked as.Therefore the research of magnesiumalloy biomaterial has been showed a new rosy prospect for the mankind.But the standard potential of magnesium is-2.375V that its chemical property is very active.Magnesiumalloy is at physiological pH (7.4-7.6) and high Cl-In the ionic surrounding medium, surperficial MgO film can be destroyed, and causes the corrosion aggravation, makes the pathological tissue healing just lose its mechanical mechanics property before; Perhaps in corrosion process, produce too much hydrogen and can't be caused the subcutaneous bubbling of surgical site by tissue absorption; And corrosion process can cause that also the pH value of body fluid raises, and possibly have a negative impact to other tissue.Simultaneously, self does not have osteoinductive magnesium, if in the direct implant into body, new bone is difficult in its surface growth.The erosion resistance of magnesium and biological activity difference have seriously limited its application as embedded material.
Summary of the invention
The objective of the invention is to the invention provides the preparation method of a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film in order to solve the problem of existing magnesiumalloy self corrosion-resistant and biological activity difference.
The preparation method of magnesium alloy surface micro-arc oxidation of the present invention/hydrothermal treatment consists composite film realizes through following steps:
One, the preparation of magnesium alloy surface micro-arc oxidation rete: the magnesiumalloy that will remove sull places electrolytic solution as anode; Stainless steel plate is as negative electrode; Carry out differential arc oxidation reaction 5～10min, it is dry more then magnesiumalloy to be taken out post-flush, obtains differential arc oxidation film layer at Mg alloy surface; Wherein, Electrolytic solution is that the sodium hydroxide of 3.5g/L～4.5g/L and six sodium polyphosphates on the high side of 4.5g/L～5g/L are formed by concentration, and solvent is a water, and the temperature of control electrolytic solution is 15～40 ℃; The micro-arc oxidation process parameter is: firm power 136W, current density is 2A/cm2, frequency is 2000Hz;
Two, the magnesiumalloy after the step 1 processing is placed the sealed reactor that fills hydro-thermal reaction liquid; Then with sealed reactor hydro-thermal reaction 1.5～2.5h under 100 ℃～160 ℃ temperature; Reaction is taken out after drying with magnesiumalloy after finishing; Obtain the biological ceramics rete at Mg alloy surface, accomplish the preparation method of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film; Wherein, hydro-thermal reaction liquid is that the sodium hydroxide of 0.03g/L～0.05g/L, the lime acetate of 0.1g/L～1.0g/L and six sodium polyphosphates on the high side of 0.1～1.2g/L are formed by concentration, and solvent is a water; Wherein, six sodium polyphosphates on the high side in step 1 and the step 2 are to be prepared according to 5: 1 mass ratio by Sodium hexametaphosphate 99 and sodium polyphosphate to obtain.
The magnesiumalloy that removes sull in the step 1 of the present invention adopts following method that sull is removed: the process of the mode of employing SiC sand paper removal sull is at first using 400 order sand papering 9min; Use 800 order sand papering 6min then; Use 1000 order sand papering 3min again; Rinse well at last, use dry back.
It is dry down at 80 ℃～100 ℃ again in the step 1 of the present invention magnesiumalloy to be taken out post-flush.
After reaction finishes in the step 2 of the present invention that magnesiumalloy taking-up back is dry down at 80 ℃～100 ℃.
Beneficial effect of the present invention is: the hydrothermal treatment consists of step 2 can be introduced calcium and phosphoric on the micro-arc oxidation films laminar surface that step 1 obtains, obtain the biological ceramics rete at Mg alloy surface, has improved the biological activity of rete.Therefore, the composite film biologically active that obtains through differential arc oxidation and hydro-thermal aftertreatment, and corrosion-resistant, ceramic membrane good uniformity, composite film is a growth in situ on matrix, and is high with substrate combinating strength.The preparation method of the present invention who utilizes differential arc oxidation and hydro-thermal post-processing technology to accomplish can carry out omnibearing processing to a large amount of complex-shaped exemplars simultaneously, does not receive the restriction of matrix size shape, and this is that other process for modifying surface institute is unapproachable.
Utilize method of the present invention to have erosion resistance and a certain bioactive composite ceramics rete what Mg alloy surface obtained, thickness reaches more than the 5.6 μ m, and roughness is more than the 0.45 μ m.After the differential arc oxidation method obtains ceramic film, utilize hydrothermal treatment consists in ceramic film, to introduce Ca, P element again, calcium element content accounts for 1.46% at most, and phosphoric accounts for 14.13% at most, has certain biological activity.For magnesiumalloy, the composite film of the biologically active that the present invention obtains is greatly improved to the corrosion resistance nature of simulated body fluid (SBF), has improved nearly 2 one magnitude.
Preparing method of the present invention combines differential arc oxidation with hydrothermal treatment consists; Utilize hydrothermal treatment consists when the micro-arc oxidation films laminar surface is introduced the calcium phosphoric; Utilize the effect of hydrothermal treatment consists simultaneously to the hole of shutoff ceramic film; Effectively stop the entering of corrosive medium, effectively improved the corrosion resistance nature of composite film.
Description of drawings
The electron scanning micrograph of Fig. 1 differential arc oxidation film layer that to be test 1 step 1 obtain at Mg alloy surface;
Fig. 2 is the electron scanning micrograph of the test 1 biological ceramics rete that obtains;
Fig. 3 is the electron scanning micrograph of the test 2 biological ceramics retes that obtain;
Fig. 4 is the electron scanning micrograph of the test 3 biological ceramics retes that prepare;
Fig. 5 is the Tafel graphic representation, and wherein, curve a is the Tafel curve of the differential arc oxidation film layer for preparing of test 2 step 1, the Tafel curve of the biological ceramics rete that the test 2 of curve b obtains, the Tafel curve of the biological ceramics rete that the test 3 of curve c obtains;
Fig. 6 is the Tafel graphic representation, and wherein, curve a is the Tafel curve of the differential arc oxidation film layer for preparing of test 2 step 1, the Tafel curve of the biological ceramics rete that the test 2 of curve b obtains, the Tafel curve of the biological ceramics rete that the test 1 of curve c obtains; The Tafel curve of the biological ceramics rete that the test 4 of curve d obtains; The Tafel curve of the biological ceramics rete that the test 5 of curve e obtains.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment is the preparation method of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film; It is realized through following steps: one, the preparation of magnesium alloy surface micro-arc oxidation rete: the magnesiumalloy that will remove sull places electrolytic solution as anode; Stainless steel plate is as negative electrode; Carry out differential arc oxidation reaction 5～20min, it is dry more then magnesiumalloy to be taken out post-flush, obtains differential arc oxidation film layer at Mg alloy surface; Wherein, Electrolytic solution is that the sodium hydroxide of 3.5g/L～4.5g/L and six sodium polyphosphates on the high side of 4.5g/L～5g/L are formed by concentration, and solvent is a water, and the temperature of control electrolytic solution is 15～40 ℃; The micro-arc oxidation process parameter is: firm power 136W, current density is 2A/cm2, frequency is 2000Hz;
Two, the magnesiumalloy after the step 1 processing is placed the sealed reactor that fills hydro-thermal reaction liquid; Then with sealed reactor hydro-thermal reaction 1.5～2.5h under 100 ℃～160 ℃ temperature; Reaction is taken out after drying with magnesiumalloy after finishing; Obtain the biological ceramics rete at Mg alloy surface, accomplish the preparation method of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film, wherein; Hydro-thermal reaction liquid is that the sodium hydroxide of 0.03g/L～0.05g/L, the lime acetate of 0.1g/L～1.0g/L and six sodium polyphosphates on the high side of 0.1～1.2g/L are formed by concentration, and solvent is a water; Wherein, six sodium polyphosphates on the high side in step 1 and the step 2 are to be prepared according to 5: 1 mass ratio by Sodium hexametaphosphate 99 and sodium polyphosphate to obtain.
The magnesiumalloy that removes sull in the step 1 of this embodiment adopts following method that sull is removed: the process of the mode of employing SiC sand paper removal sull is at first using 400 order sand papering 9min; Use 800 order sand papering 6min then; Use 1000 order sand papering 3min again; Rinse well at last, use dry back.
The beneficial effect of this embodiment is: the ceramic film biologically active that obtains through differential arc oxidation and hydro-thermal aftertreatment, and corrosion-resistant, ceramic membrane good uniformity, ceramic film is a growth in situ on matrix, and is high with substrate combinating strength.Utilize the preparation method of this embodiment of differential arc oxidation and hydro-thermal post-processing technology, can carry out omnibearing processing to a large amount of complex-shaped exemplars simultaneously, do not receive the restriction of matrix size shape, this is that other process for modifying surface institute is unapproachable.
The biological ceramics rete that utilizes the method for this embodiment to obtain at Mg alloy surface, thickness reaches more than the 5.6 μ m, and roughness is more than the 0.45 μ m.After the differential arc oxidation method obtains ceramic film, utilize hydrothermal treatment consists in ceramic film, to introduce Ca, P element again, calcium element content accounts for 1.46% at most, and phosphoric accounts for 14.13% at most, has certain biological activity.For magnesiumalloy, the biological ceramics rete that this embodiment obtains is greatly improved to the corrosion resistance nature of simulated body fluid (SBF), has improved 2 one magnitude.
The preparation method of this embodiment combines differential arc oxidation with hydrothermal treatment consists; Utilize hydrothermal treatment consists when the micro-arc oxidation films laminar surface is introduced the calcium phosphoric; Utilize the effect of hydrothermal treatment consists simultaneously to the hole of shutoff ceramic film; Effectively stop the entering of corrosive medium, effectively improved the corrosion resistance nature of composite film.
Embodiment two: what this embodiment and embodiment one were different is that electrolytic solution is the sodium hydroxide of 3.8g/L～4.2g/L and six sodium polyphosphates on the high side of 4.6g/L～4.9g/L by concentration in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is that electrolytic solution is the sodium hydroxide of 4g/L and six sodium polyphosphates on the high side of 4.8g/L by concentration in the step 1.Other step and parameter are identical with embodiment one.
Embodiment four: this embodiment and embodiment one, two or three are different is that in the step 1 magnesiumalloy to be taken out post-flush dry down at 80 ℃～100 ℃ again.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: what this embodiment was different with one of embodiment one to four is with sealed reactor hydro-thermal reaction 1.8～2.3h under 120 ℃～150 ℃ temperature in the step 1.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to four is with sealed reactor hydro-thermal reaction 2h under 140 ℃ temperature in the step 1.Other step and parameter are identical with one of embodiment one to four.
Embodiment seven: what this embodiment was different with one of embodiment one to six is that reaction solution is that the sodium hydroxide of 0.035g/L～0.045g/L, the lime acetate of 0.1g/L～0.5g/L and six sodium polyphosphates on the high side of 0.12～0.5g/L are formed by concentration in the step 2, and solvent is a water.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what this embodiment was different with one of embodiment one to six is that reaction solution is that the sodium hydroxide of 0.04g/L, the lime acetate of 0.3g/L and six sodium polyphosphates on the high side of 0.16g/L are formed by concentration in the step 2, and solvent is a water.Other step and parameter are identical with one of embodiment one to six.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is after reaction finishes in the step 2 that magnesiumalloy taking-up back is dry down at 80 ℃～100 ℃.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is that micro-arc oxidation process adopts the diphasic pulse power supply in the step 1; Processing parameter is: firm power 136W; Frequency is 2000Hz, and dutycycle is 10%, and forward current density is 2A/cm2Other step and parameter are identical with one of embodiment one to nine.
In order to verify beneficial effect of the present invention, test as follows:
Test 1: the preparation method of Mg alloy surface biological ceramics rete; It is realized through following steps: one, the preparation of magnesium alloy surface micro-arc oxidation rete: the magnesiumalloy that will remove sull places electrolytic solution as anode; Stainless steel plate is as negative electrode; Carry out differential arc oxidation reaction 5min, it is dry more then magnesiumalloy to be taken out post-flush, obtains differential arc oxidation film layer at Mg alloy surface; Wherein, electrolytic solution is that the sodium hydroxide of 4g/L and six sodium polyphosphates on the high side of 4.8g/L are formed by concentration, and solvent is a water; The temperature of control electrolytic solution is 15～40 ℃; Micro-arc oxidation process adopts the diphasic pulse power supply, and processing parameter is: firm power 136W, and frequency is 2000Hz; Dutycycle is 10%, and forward current density is 2A/cm2
Two, the magnesiumalloy after the step 1 processing is placed the sealed reactor that fills hydro-thermal reaction liquid; Then with sealed reactor hydro-thermal reaction 2h under 120 ℃ temperature; Reaction is taken out after drying with magnesiumalloy after finishing; Obtain the biological ceramics rete at Mg alloy surface, accomplish the preparation method of Mg alloy surface biological ceramics rete; Wherein, hydro-thermal reaction liquid is that the sodium hydroxide of 0.04g/L, the lime acetate of 0.3g/L and six sodium polyphosphates on the high side of 0.16g/L are formed by concentration, and solvent is a water; Wherein, six sodium polyphosphates on the high side in step 1 and the step 2 are to be prepared according to 5: 1 mass ratio by Sodium hexametaphosphate 99 and sodium polyphosphate to obtain.
The magnesiumalloy that adopts in the test 1 is distortion AZ31B magnesiumalloy.
The step 1 of test 1 is 6.91 μ m at the thickness of the differential arc oxidation film layer that Mg alloy surface obtains.
The thickness of the biological ceramics rete that after step 1 and step 2 processing, obtains in the test 1 is 6.24 μ m.
The step 1 of test 1 is as shown in Figure 1 at the electron scanning micrograph of the differential arc oxidation film layer that Mg alloy surface obtains; It is thus clear that; The top layer of the differential arc oxidation film layer that only obtains through the differential arc oxidation of step 1 is sparse; Hole is very big, and the sign that comes off is arranged, and the roughness of differential arc oxidation film layer is 0.693 μ m.The electron scanning micrograph of the biological ceramics rete that obtains through the processing of step 1 and step 2 is as shown in Figure 2; It is thus clear that; The top layer of the biological ceramics rete that differential arc oxidation film layer obtains after hydrothermal treatment consists is neatly fine and close, and hole obviously diminishes, and roughness is reduced to 0.433 μ m.
The erosion resistance of biological ceramics rete in the SBF simulated body fluid that test 1 prepares tested, and its Tafel curve is shown in curve c among Fig. 6.The fitting data of its Tafel curve is as shown in table 3.
Test 2: this test is with the difference of test 1, in the step 2 magnesiumalloy after the step 1 processing is placed the sealed reactor that fills hydro-thermal reaction liquid, then with sealed reactor hydro-thermal reaction 2h under 140 ℃ temperature.Other step and parameter are identical with test 1.
The thickness of the biological ceramics rete that after step 1 and step 2 processing, obtains in the test 2 is 5.31 μ m.
The electron scanning micrograph of the biological ceramics rete that obtains through the processing of step 1 and step 2 is as shown in Figure 3; It is thus clear that; The top layer of the biological ceramics rete that differential arc oxidation film layer obtains after hydrothermal treatment consists is neatly fine and close, and hole obviously diminishes, and roughness is reduced to 0.486 μ m.
Carry out gamma-spectrometric data analysis (EDS) to testing the 2 biological ceramics retes that obtain, drawn element and content thereof in the biological ceramics rete, as shown in table 1.
To testing the erosion resistance test of differential arc oxidation film layer in the SBF simulated body fluid that 2 step 1 prepare, the Tafel curve that test obtains is shown in curve a among Fig. 5.Test testing 2 erosion resistances of biological ceramics rete in the SBF simulated body fluid that obtain simultaneously, its Tafel curve is shown in curve b among Fig. 5.Visible by Fig. 5, the erosion resistance of the biological ceramics rete after hydrothermal treatment consists is greatly improved, and corrosion electric current density has reduced nearly 2 one magnitude.It is thus clear that, after the hydrothermal treatment consists shutoff hole of film surface, can effectively stop the entering of corrosive medium, explain that the hydro-thermal aftertreatment has reached the effect that improves the rete corrosion resistance nature.The fitting data of Tafel curve is as shown in table 2.
Test 3: simultaneous test, differently with test 2 be, hydro-thermal reaction liquid is the sodium hydroxide solution of concentration 0.04g/L in the step 2, solvent is a water.Other step and parameter are identical with test 2.
The electron scanning micrograph of the biological ceramics rete that test 3 prepares is as shown in Figure 4, compares with the biological ceramics rete (see figure 3) that test 2 prepares, and the surface of the biological ceramics rete that test 2 prepares is more neat fine and close, and hole is littler.
Carry out gamma-spectrometric data analysis (EDS) to testing the 3 biological ceramics retes that obtain, drawn element and content thereof in the biological ceramics rete, as shown in table 1.
Test testing 3 erosion resistances of biological ceramics rete in the SBF simulated body fluid that obtain, its Tafel curve is shown in curve c among Fig. 5.The fitting data of its Tafel curve is as shown in table 2.
Table 1 is element and content thereof in test 2 and the test 3 biological ceramics retes that obtain, and wherein % is the quality percentage composition.
Table 1
| O(％) | Na(％) | Mg(％) | Al(％) | P(％) | Ca(％) | |
| Test 2 | 55.60 | 1.42 | 31.61 | 0.39 | 10.82 | 0.17 |
| Test 3 | 57.35 | 1.79 | 31.10 | 0.47 | 9.23 | 0.05 |
Visible by table 1, can be through hydrothermal treatment consists at the inner calcium constituent of introducing of differential arc oxidation film layer, phosphoric is mainly from the differential arc oxidation stage.
The biological ceramics rete that table 2 is differential arc oxidation film layers of obtaining of test 2 step 1, test 2 obtains and test the fitting data table of the Tafel curve of the 3 biological ceramics retes that obtain.
Table 2
Test 4: this test with test 1 different be in the step 2 magnesiumalloy after the step 1 processing to be placed the sealed reactor that fills hydro-thermal reaction liquid, then with sealed reactor hydro-thermal reaction 2h under 100 ℃ temperature.Other step and parameter are identical with test 1.
The thickness of the biological ceramics rete that after step 1 and step 2 processing, obtains in the test 4 is 6.49 μ m.
The top layer of the biological ceramics rete that obtains through the processing of step 1 and step 2 is neatly fine and close, and hole obviously diminishes, and roughness is reduced to 0.517 μ m.
Test testing 4 erosion resistances of biological ceramics rete in the SBF simulated body fluid that obtain, its Tafel curve is shown in curve d among Fig. 6.The fitting data of its Tafel curve is as shown in table 3.
Test 5: this test with test 1 different be in the step 2 magnesiumalloy after the step 1 processing to be placed the sealed reactor that fills hydro-thermal reaction liquid, then with sealed reactor hydro-thermal reaction 2h under 160 ℃ temperature.Other step and parameter are identical with test 1.
The thickness of the biological ceramics rete that after step 1 and step 2 processing, obtains in the test 5 is 3.6 μ m.
The top layer of the biological ceramics rete that obtains through the processing of step 1 and step 2 is neatly fine and close, and hole obviously diminishes, and roughness is reduced to 0.488 μ m.
Test testing 5 erosion resistances of biological ceramics rete in the SBF simulated body fluid that obtain, its Tafel curve is shown in curve e among Fig. 6.The fitting data of its Tafel curve is as shown in table 3.
Curve a is the Tafel curve of the differential arc oxidation film layer for preparing of test 2 step 1 among Fig. 6, and curve b is the Tafel curve of the biological ceramics rete for preparing of test 2.
The biological ceramics rete that table 3 is differential arc oxidation film layers of preparing of test 2 step 1, test 2 obtains, the biological ceramics rete that test 1 obtains, biological ceramics rete that test 4 obtains and test the fitting data table of the Tafel curve of the 5 biological ceramics retes that obtain.
Table 3
Visible by table 3, be that the corrosion resisting property of the biological ceramics rete that obtains of 140 ℃ of hydrothermal treatment consists is much better than other temperature in temperature.The hydrothermal treatment consists of other temperature raises along with temperature to the raising degree of membranous layer corrosion resistance and strengthens.This is that 140 ℃ of hydrothermal treatment consists are best to the hole effect of shutoff rete, has effectively stoped the entering of corrosive medium.
Wherein, adopt TT260 coating thickness tester to carry out the thicknesses of layers test in test 1 to the test 5; Utilize the energy depressive spectroscopy of JSM-6480A type sem and outfit thereof, the relative content of element in research Micro-Arc Oxidized Ceramic Coating surface topography and the rete; Utilize the corrosion resistance nature of CHI604C electrochemical analyser test rete in the SBF simulated body fluid, test parameter is: adopt three-electrode system, reference electrode is SCE (being abbreviated as SCE); Supporting electrode is a platinum electrode; Sample is a working electrode, and test area 1cm2, sample place simulated body fluid (SBF); The polarization curve scanning speed is 1mV/s, and sweep limit is about electrode system open circuit potential ± 0.5V.For the polarization curve that test obtains, utilize electrochemistry to resolve the average corrosion electric current density (i of computed in softwareCorrAnd corrosion potential (ECorr).Match as a result obtains anode/cathode Tafel slope (b according to the test gainedaAnd bc), be based on the approximately linear polarization under the corrosion potential, polarization resistance (Rp) value determine by following relation:
Claims (10)
1. the preparation method of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film; The preparation method who it is characterized in that magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film; It is realized through following steps: one, the preparation of magnesium alloy surface micro-arc oxidation rete: the magnesiumalloy that will remove sull places electrolytic solution as anode; Stainless steel plate is as negative electrode; Carry out differential arc oxidation reaction 5～20min, it is dry more then magnesiumalloy to be taken out post-flush, obtains differential arc oxidation film layer at Mg alloy surface; Wherein, Electrolytic solution is that the sodium hydroxide of 3.5g/L～4.5g/L and six sodium polyphosphates on the high side of 4.5g/L～5g/L are formed by concentration, and solvent is a water, and the temperature of control electrolytic solution is 15～40 ℃; The micro-arc oxidation process parameter is: firm power 136W, current density is 2A/cm2, frequency is 2000Hz;
Two, the magnesiumalloy after the step 1 processing is placed the sealed reactor that fills hydro-thermal reaction liquid; Then with sealed reactor hydro-thermal reaction 1.5～2.5h under 100 ℃～160 ℃ temperature; Reaction is taken out after drying with magnesiumalloy after finishing; Obtain the biological ceramics rete at Mg alloy surface, accomplish the preparation method of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite film, wherein; Hydro-thermal reaction liquid is that the sodium hydroxide of 0.03g/L～0.05g/L, the lime acetate of 0.1g/L～1.0g/L and six sodium polyphosphates on the high side of 0.1～1.2g/L are formed by concentration, and solvent is a water; Wherein, six sodium polyphosphates on the high side in step 1 and the step 2 are to be prepared according to 5: 1 mass ratio by Sodium hexametaphosphate 99 and sodium polyphosphate to obtain.
2. the preparation method of a kind of magnesium alloy surface micro-arc oxidation according to claim 1/hydrothermal treatment consists composite film is characterized in that electrolytic solution is the sodium hydroxide of 3.8g/L～4.2g/L and six sodium polyphosphates on the high side of 4.6g/L～4.9g/L by concentration in the step 1.
3. the preparation method of a kind of magnesium alloy surface micro-arc oxidation according to claim 1/hydrothermal treatment consists composite film is characterized in that electrolytic solution is the sodium hydroxide of 4g/L and six sodium polyphosphates on the high side of 4.8g/L by concentration in the step 1.
4. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films, it is dry down at 80 ℃～100 ℃ again to it is characterized in that in the step 1 magnesiumalloy being taken out post-flush.
5. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films, it is characterized in that in the step 1 sealed reactor hydro-thermal reaction 1.8～2.3h under 120 ℃～150 ℃ temperature.
6. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films, it is characterized in that in the step 1 sealed reactor hydro-thermal reaction 2h under 140 ℃ temperature.
7. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films; It is characterized in that reaction solution is that the sodium hydroxide of 0.035g/L～0.045g/L, the lime acetate of 0.1g/L～0.5g/L and six sodium polyphosphates on the high side of 0.12～0.5g/L are formed by concentration in the step 2, solvent is a water.
8. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films; It is characterized in that reaction solution is that the sodium hydroxide of 0.04g/L, the lime acetate of 0.3g/L and six sodium polyphosphates on the high side of 0.16g/L are formed by concentration in the step 2, solvent is a water.
9. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films, it is characterized in that after reaction finishes in the step 2 magnesiumalloy taking-up back is dry down at 80 ℃～100 ℃.
10. according to the preparation method of claim 1,2 or 3 described a kind of magnesium alloy surface micro-arc oxidation/hydrothermal treatment consists composite films; It is characterized in that micro-arc oxidation process adopts the diphasic pulse power supply in the step 1; Processing parameter is: firm power 136W; Frequency is 2000Hz, and dutycycle is 10%, and forward current density is 2A/cm2
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